Keto carboxylic acid esters and process of manufacture



Patented J... 17,1939

umrco, STATES 'KETO CARBOXYLIG ACID ESTERS AND PROCESS OF MANUFACTURE I,Ivan Gubelmann, .Wihnington, Del., assignor to No Drawing.

. E. I. du Pont de Nemours & Company, Wilmington, DeL, a corporation ofDelaware Application March 24, 1938,

Serial No. 197,962

' s Claims. (01. 260-469) This invention relatesto-new chemicalcompounds. More especially it relates to new keto carboxylic acidesters, which are useful in the field of synthetic resins and elsewhere.i5 In the copending. application of Sachs Ser. No. 197,869, filed March24, 1938 there is disclosed and claimed a group of new keto carboxylicacids having the general formula wherein R is an aryl radical.

It is an object of this invention to prepare new organic chemicalcompounds. It is a further object to prepare new keto carboxylic acidesters. A still further object is to prepare esters of the 25 abovedescribed acids.

These objects are accomplished by reacting the above described ketocarboxylic acids with alcohols, preferably in the presence ofan'esterification catalyst 30 The following example, in whichthequantities of materials are specified as parts by weight, is setforth by way of specific illustration. but the invention is not limitedthereto as will become more fully apparent hereinafter.

35 .1. I Example A keto carboxylic acid of the formula HO CH2 CHCOOH IOH lation. The remaining product is a viscous oil soluble in the usualorganic solvents.

The keto carboxylic acids suitable for the process of the invention arethose of the general formula given above in which R is an aryl radi- 5cal, such, for example, as phenyl, naphthyl or anthracyl. 'I'hisradicalmay be substituted or unsubstituted. Preferably R is a radicalof amember of the benzene series. By way of specific example may bementioned 'phenyl, tolyl, xylyl, 10 chloro and bromo phenyl, methoxyphenyl, ethoxy phenyl, naphthyl, anthracyl, etc.

Any alcohol is suitable for the process of the present invention. Thepreferred alcohols are primary and secondary monohydric, andunsubstituted and substituted polyhydric alcohols. By way of specificexamples may be mentioned methyl, ethyl, propyl, butyl, amyl, benzyl andbornyl alcohols, ethylene glycol, propylene glycol, glycerol, glycericmonochlor hydrin, glyceric monoethyl ether, glycol mono alkyl ethers,etc.

The process of preparing the esters may be varied within wide limits oftemperature and pressure. Where low boiling alcohols are reacted,somewhat elevated pressure during the esterification is advantageous.While it is preferred to use an esterification catalyst such, forexample, as dry hydrogen chloride, sulfuric acid; para toluene sulfonicacid, etc., the process may be carried out in the absence of a catalyst.

The new keto carboxylic acid esters obtained by this invention areuseful as resins, plastic masses or softeners. By systematic'variationof the aromatic radical and/or the alcohol component, the

physical properties of the final products may be I claim: 1. A chemicalcompound of the formula CH3 5 HO (JHa CH-dd-R Ho\('JH/oH- 1v 0 l CH CH3CH3 wherein R is aryl and R is an esterification residue of an alcohol.

2. A chemical compound of the formula 6. The process which comprisesreacting a CH; primary monohydric alcohol with a keto car- I boxylicacid of the formula 5 I! CHI 5 1 v V A H (3B, on-o-n CH HO OH: CH-COOH10 om \GH3 wherein R is an aryl radical of the benzene series I V CH andR 1s an esterification residue of a prlmary g C s CH:

monohydric alcohol.

1 3. A chemical compound of the formula 5 OH; wherein R-is "an arylradical of the benzene 1 series. I\ o 7. The process which comprisesreacting a sec- H0 CH JL ondary monohydric alcohol with a keto car- 20 2v l boxylic acid of the formula .110 CH: CH(I"TR' 2 O I cm 5 t v t I I 7CH3 CH3 I Hi} (13H; CH'C'-'R wherein R is an aryl radical of the benzeneseries l and'R' is an esterification residue of a secondary \T COOHmonohydric alcohol. 0 30 {1. A chemical compound of the formula H I 7CH:

v 7 0H; CH5 C V I? 1 wherein R 1s an aryl radical of the benzene 35 I 1l a series.

V T V V V Y 8. The process which comprises reacting a C 0 polyhydricalcohol with a keto carboxylic acid 7 I of the formula V E on I a 40 OH:CH: l 3 wherein Ris an aryl radical of the benzene series 253212115 anestern'ication residue of a polyhydrlc E I 5. The process whichcomprises reacting an HO CEFCOOH alcohol with a keto carboxylic acid ofthe formula I (3H3 a H0 OH: OHC-R V m": :112 nf-coon wherein R is anaryl radical of the benzene series.

0 (13H) IVAN GUBELMANN. 55

wherein R is aryl.

